Migration Properties and Structure of Phosphate Glasses Containing Alkali Metal Sulfates

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Abstract

The paper investigates a set of physico-chemical properties of glasses of the M2O–MPO3, M2SO4–MPO3 (M = Li, Na) systems and glasses of the same systems in which one alkali metal was replaced by another. All compositions were obtained using mortar technology in the manufacture of the initial charge. It was found that almost all the properties of the studied glasses differ slightly in their characteristics from the properties of glasses of similar compositions obtained using solid starting components. It is shown that the electrical properties of pure phosphate and phosphate-sulfate glasses with a commensurate volume concentration of the main current carriers, alkaline cations, are close, i. e. the presence of sulfate ions in mixed glass increases the electrical parameters insignificantly. The equivalent substitution of lithium cations for sodium cations in phosphate and phosphate-sulfate glasses is accompanied by a polychelic effect – a nonlinear change in electrical parameters, and in the phosphate-sulfate system (with a close volume concentration of current carrier ions) this effect is more pronounced.

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About the authors

E. V. Bochagina

Peter the Great St. Petersburg Polytechnic University

Email: irina.s.yaroshenko@gmail.com
Russian Federation, St. Petersburg, 195251

V. V. Polyakova

Peter the Great St. Petersburg Polytechnic University

Email: irina.s.yaroshenko@gmail.com
ORCID iD: 0000-0003-4381-9836
Russian Federation, St. Petersburg, 195251

I. A. Sokolov

Peter the Great St. Petersburg Polytechnic University; I. V. Grebenshchikov Institute of Silicate Chemistry – branch of the National Research Center “Kurchatov Institute” – PNPI

Email: irina.s.yaroshenko@gmail.com
ORCID iD: 0000-0002-3904-3409
Russian Federation, St. Petersburg, 195251; St. Petersburg, 199034

I. S. Yaroshenko

Peter the Great St. Petersburg Polytechnic University

Author for correspondence.
Email: irina.s.yaroshenko@gmail.com
ORCID iD: 0000-0001-5775-6878
Russian Federation, St. Petersburg, 195251

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Supplementary files

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2. Fig. 1. IR spectra of glasses of Li2O–LiPO3 and Li2SO4–LiPO3 systems. 1 – glassy LiPO3, 2 – 0.1Li2O⋅0.9LiPO3, 3 – 0.18Li2SO4⋅0.82LiPO3, 4 – 0.27Li2SO4⋅0.73LiPO3.

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3. Scheme 1.

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4. 2. Concentration dependence of electrical conductivity (at 293 K) in glasses of Li2SO4–LiPO3 (1) and Li2O–LiPO3 (2) systems [4, 19].

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5. 3. IR spectra of glassy sodium metaphosphate NaPO3 (1) and glass composition 0.24Na2SO4⋅0.76NaPO3 (2).

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6. 4. Electrical properties of glasses of Na2SO4–NaPO3 (1) and Na2O–NaPO3 (2) systems.

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7. Scheme 2.

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8. Scheme 3.

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9. Fig. 5. Dependence of changes in electrical conductivity and activation energy of electrical conductivity on the composition of equivalent substitution of Li+ ions for Na+ ions in glasses of xLiPO3–(1–x) systemsNaPO3(1) and x(0.18Li2SO4× 0.82LiPO3)–(1–x)(0.19Na2SO4⋅0.81NaPO3) (2), here 0 x 1.

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